Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D157/00—Coating compositions based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
  • Y10T428/31587—Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

Definitions

• the invention relates to water-thinnable, air-drying coating compositions based on combinations of water-thinnable alkyd resins with aqueous polymer dispersions and maleated oils or fatty acids.
• the products serve, if necessary after incorporation of pigments, fillers and / or paint auxiliaries or paint additives corresponding to the respective intended use, as coating agents for wood and metal substrates, in particular for paint coats and wood glazes.
• the coating compositions of the invention are easy to process and give films with excellent flow, high elasticity and excellent weather resistance. Wood glazes formulated from this show good penetration and protection.
• the content of organic auxiliary solvents can be reduced to below 5% by weight of the volatile paint content.
• Alkyd resins as described in EP 0 295 403 A 2 are used as component (A) of the combination according to the invention.
• alkyd resins have a free acid group content corresponding to an acid number of 25 to 70 mg KOH / g, these acid groups deriving at least 80% from methacrylic acid units, which together with other vinyl and / or (meth) acrylic monomers in a separate reaction step Part of the unsaturated fatty acids used were grafted on.
• the content of drying and / or semi-drying fatty acids is between 30 and 70% by weight.
• a proportion of 10 to 40% by weight, based on the resin weight, of these fatty acids is introduced in the form of the fatty acid-methacrylic acid copolymer.
• the alkyd resins further contain 10 to 25% by weight of polyalcohols with 2 to 6 hydroxyl groups, 10 to 20% by weight of aromatic and / or aliphatic dicarboxylic acids, 0 to 15% by weight of cyclic and / or polycyclic monocarboxylic acids and 0 up to 5% by weight of a polyethylene glycol.
• the end products have an intrinsic viscosity between 7 and 16 ml / g, measured in chloroform at 20 ° C.
• unsaturated fatty acids with an iodine number above 135 (preferably 160-200) and with a predominantly isolated position of the double bonds are used.
• Linseed oil fatty acid, safflower fatty acid and the fatty acids of hemp, lallemantia, perilla and stilling oil are suitable, optionally in a mixture with up to 25% by weight of dehydrated castor oil fatty acid or a comparable, conjugated fatty acid produced by isomerization.
• the fatty acid graft copolymers are composed of 30 to 50% by weight of the abovementioned fatty acids, 10 to 25% by weight of methacrylic acid and 30 to 55% by weight of other monomers which, apart from the CC double bond, have no further functional groups, where the sum of the percentages must be 100.
• Monomers which are used in addition to methacrylic acid are preferably (meth) acrylic compounds and vinyl compounds, with the proviso that at least 80% by weight consist of those which form gasoline-soluble homopolymers.
• Vinyltoluene is used to adjust the optimal film hardness of the copolymer.
• monomers which form gasoline-insoluble polymers, such as methyl methacrylate or styrene, can also be used.
• the graft copolymerization is carried out in such a way that the majority of the fatty acid, if appropriate in the presence of small amounts of inert solvents, is heated to 110-150 ° C. and the mixture of monomers is metered in with a suitable initiator and the remaining fatty acid over the course of a few hours. The reaction mixture is then kept at the reaction temperature until a residue determination gives a polymerization conversion of over 95%.
• Suitable initiators include di-tert-butyl peroxide, tert-butyl perbenzoate and cumene hydroperoxide.
• the fatty acid-methacrylic acid graft copolymers prepared in this way are processed together with further fatty acids to form water-soluble alkyd resins.
• Vegetable and animal fatty acids with an iodine number above 120 can be used as fatty acids in this stage, with a part of the double bonds preferably being in the conjugated position.
• Suitable polyols and dicarboxylic acids for the production of the alkyd resins are all products which are also used for the production of conventional alkyd resins.
• Trimethylolethane, trimethylolpropane, pentaerythritol and sorbitol are preferably used as polyols and ortho- or isophthalic acid and adipic acid as dicarboxylic acids.
• Cyclic or polycyclic monocarboxylic acids, such as resin acids or benzoic acid can also be used to regulate the film hardness. If necessary, proportions of up to 5% by weight of polyethylene glycols with a molecular weight of 1000 to 3000 can also be incorporated.
• the esterification can be carried out by heating all components together.
• high-melting raw materials such as pentaerythritol and isophthalic acid
• the esterification is then carried out so far that the final value of the acid number corresponds to approximately 90% of the concentration of the carboxyl groups of methacrylic acid.
• Particularly suitable organic, water-compatible co-solvents are the methyl, ethyl and butyl ethers of ethylene glycol, diethylene glycol, 1,2-propylene glycol and dipropylene glycol. In some cases, only water-compatible solvents such as n- and iso-butanol can be used. The total content of organic solvents in the finished paint should be kept as low as possible.
• Triethylamine, dimethylethanolamine, KOH, NaOH and LiOH are suitable.
• the alkyd resins can be used either in neutralized or non-neutralized form in a solution in water-compatible solvents.
• products are preferably used in the form of aqueous emulsions, since the content of organic solvents can thereby be significantly reduced.
• Component (A) is based on the sum of the binders, i.e. H. of components (A) to (C), in an amount of 4 to 95 wt .-%.
• the combination (A) to (C) preferably contains at least 30% by weight of this component.
• Aqueous polymer dispersions based on (meth) acrylic ester and / or butadiene and / or styrene copolymers and also polyurethane dispersions are used as component (B). Products of this type are under various brand names commercially available.
• Examples are: MOWILITH VSW 6866, MOWILITH DM 772 (acrylate copolymer dispersions from HOECHST AG), NEOCRYL XK 62 (styrene-acrylate copolymer dispersions from POLYVINYL CHEMIE), ACRONAL 603 (acrylate dispersions from BASF AG), LITEX CA (styrene-butadiene copolymers from Chem Werke Hüls AG), DAOTAN VTW 1210 (polyurethane dispersion from HOECHST AG) All listed product names are registered trademarks of the named manufacturers.
• Component (B) is based on the sum of the binders, i.e. H. of components (A) to (C), in an amount of 4 to 95 wt .-%.
• the combination preferably contains at least 20% by weight of this component.
• Component (C) which is used in an amount of 1 to 30% by weight, preferably 5 to 20% by weight, based on the sum of the binders, is an adduct of maleic anhydride with drying oils or with , such oils constituting unsaturated fatty acids and / or to hydroxyl-free, synthetically produced esters of these fatty acids with diols or polyols.
• the anhydride structures are opened before neutralization by reaction with water and / or monoalcohols with 1 to 10 carbon atoms.
• the raw materials for these adducts and the processes for their preparation are known from the literature.
• the proportion of maleic anhydride in the adducts suitable for the present invention is between 5 and 30% by weight, preferably between 7.5 and 25% by weight, based on the adduct.
• the coating agents can contain the usual pigments and fillers, as well as paint auxiliaries or paint additives. The selection or the amount of this component depends on the respective application of the coating agent.
• Components (A) and (C) are preferably mixed after the neutralization of the carboxyl groups. Component (B) is then added, if appropriate after adding part of the water intended for dilution.
• a suitable reaction vessel 200 parts of safflower fatty acid, 110 parts of isomerized linoleic acid (approx. 50% 9,11-linoleic acid), 115 parts of pentaerythritol and 100 parts of isophthalic acid are esterified at 230 ° C. until a clear melt has formed. After a further hour, 340 g of fatty acid copolymer A 1 are added and the reaction is carried out at 200 ° C. until the specified end values are reached. After the inert solvent has been stripped off (from the copolymer), the batch is adjusted to a solids content of 87% using ethylene glycol monobutyl ether and emulsified at 50 ° C.
• the amount of ammonia and water is chosen so that a pH of the emulsion of 8.2 to 8.4 and a solids content of 40% results.
• the resin solution is a milky to transparent liquid with a pronounced structural viscosity.
• component (II) The following commercially available polymer dispersions are used as component (B) :
• Component (C1) 700 parts of soybean oil and 100 parts of maleic anhydride are reacted in a suitable reaction vessel at 200 to 210 ° C. until no free maleic anhydride can be detected. After cooling to 110 ° C., 162 parts of diethylene glycol monobutyl ether and 3 parts of triethylamine are added and the reaction is carried out up to an acid number of approximately 55 mg KOH / g. The product is diluted to a solids content of 90% with methoxypropoxypropanol.
• Component (C2) In the same way as described in (C1), an adduct is prepared from 280 parts of linseed oil fatty acid and 100 parts of maleic anhydride, the anhydride groups of which are opened at 80 ° C. with 35 parts of methanol in the presence of 3 parts of triethylamine.
• the product has an acid number of approx. 240 mg KOH / g and is diluted to a solids content of 90% with methoxypropoxypropanol.
• Component (C3) A mixture of 150 parts of dehydrated castor oil and 150 parts of linseed oil are stirred under an inert gas at 250 ° C. for one hour and then reacted at 200 ° C. with 100 parts of maleic anhydride. The anhydride groups are opened at about 100 ° C. with 162 parts of diethylene glycol monobutyl ether in the presence of 2 parts of triethylamine. The reaction product (acid number approx. 90 mg KOH / g) is diluted to a solids content of 90% with methoxypropoxypropanol.
• Pigment grinds with component (A) with the following composition are produced on an agitator ball mill:
• Example 1 83 parts
• Example 2 115 parts Component (A), 40%
• Example 3 177.5 parts 1.5 parts Ammonia solution 25% 100 parts Titanium dioxide (rutile) 1 teaspoon Combination dryer can be diluted with water (Co, Ba, Zr) 2 parts
• Anti-skin agent (oxime base) 1 teaspoon Defoamer (silicone-free) 30 parts water
• the pigment-binder ratio of this pigment paste is 3: 1, 2: 1 and 1: 0.7.
• Comparative example V (a) contains no component (C).
• the lacquers After adjusting the pH to 8.8 - 9.1 with ammonia solution, the lacquers are applied to sanded softwood boards.
• Water-thinnable wood glazes were prepared in accordance with the following formulations (Table 3)
• the glazes have a solids content of approx. 35%. After setting the pH to 9.2 and a run-out time of 30 to 35 seconds (DIN 53211/20 ° C), the glaze is applied by brushing on spruce boards. Comparative example V (c) was formulated without an adduct component (component C). As a further comparison product (example V (d)), a commercially available water-dilutable wood glaze was tested.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Paints Or Removers (AREA)

Applications Claiming Priority (2)

Publications (3)

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• 1988
  • 1988-08-31 AT AT0213188A patent/AT390799B/de not_active IP Right Cessation
• 1989
  • 1989-08-22 NO NO893372A patent/NO306120B1/no not_active IP Right Cessation
  • 1989-08-25 EP EP89115663A patent/EP0356920B1/de not_active Expired - Lifetime
  • 1989-08-25 DE DE8989115663T patent/DE58904262D1/de not_active Expired - Fee Related
  • 1989-08-29 DD DD89332162A patent/DD284685A5/de not_active IP Right Cessation
  • 1989-08-30 CA CA000609889A patent/CA1339431C/en not_active Expired - Fee Related
  • 1989-08-30 US US07/400,787 patent/US4996250A/en not_active Expired - Fee Related
  • 1989-08-31 DK DK198904322A patent/DK174046B1/da not_active IP Right Cessation

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